Siltolylene compounds



United States Patent 3,387,015 SILTOLYLENE COMPOUNDS William A. Piccoli, Pittsburgh, Pa., assignor to Dow Corning Corporation, Midland, Mich., a corporation of Michigan No Drawing. Filed Apr. 26, 1965, Ser. No. 451,061 6 Claims. (Cl. 260-4483) This application relates to silcarbanes in which one silicon -is attached to a carbon of a methylene group and the other a carbon atom to a phenyl ring.

The compositions of this invention are useful as water repellents as dielectric fluids and as resinous and rubbery compositions.

This invention relates to a compound of the formula I I'll CHgSiX SIX in which R is a monovalent hydrocarbon radical or a radical of the formula RCH CH in which R is perfluoroalkyl radical and X is H, alkoxy or OH.

The above compounds are best prepared by reacting a-o-dichlorotoluene, a silane of the formula R SiXCl, in

'which R and X are as above defined, and magnesium in a suitable ether solvent such as tetrahydrofuran. The reaction is best carried out in an inert atmosphere such as nitrogen and at a temperature of from 30 to 100 C. It should be understood that the temperature is not critical so long as it is suflicient to cause the reaction to go at a reasonable rate.

Those compounds in which X is OH are best prepared by hydrolysis of the SiH or the alkoxy compounds in the conventional manner for hydrolyzing such compounds.

This invention also relates to cyclic compounds of the formula III -Si CHlSlO- 8 in which R is as above defined. Any remaining units in said polymer are of the formula R",.s1o

in which R" is a monovalent hydrocarbon radical or a monovalent halo-hydrocarbon radical and n is an integer from 0-3 inclusive. V

The polymeric compounds of this invention can be homopolymeric or copolymeric materials. Homopolymers and copolymers in which all of the polymer units have the structure III are best prepared by condensation of the corresponding diols I in the absence of a solvent. This condensation can be carried out with any of the wellknown silanol condensation catalysts such as amine salts of carboxylic acids such as tetramethyl guanidine-2-ethylhexoate or alkali metal phenoxides such as sodium phenoxide or salts of heavy metals such as stannous octoate or dibutyl tin dilaurate.

Those copolymers which contain III type units together with units can be prepared either by the copolymerization of diols I with diols of the formula or they can be prepared by the copolymerization of the cyclic Compounds II with cyclic compounds of the formula (R" SiO) or they can be prepared by the co-hydrolysis and co-condensation of alkoxy silanes of the Formula I with silanes' of the formula R",,SiZ in which Z is a hydrolyzable group. Any of the above procedures can be carried out in the conventional manner for copolymerizing and/or cohydrolyzing organosilicon compounds.

For the purpose of this invention, R can be any monovalent hydrocarbon radical such as alkyl radicals such as methyl, ethyl, butyl, octadecyl or isopropyl; alkenyl radicals such as vinyl, allyl, hexenyl and octadecenyl; cycloaliphatic hydrocarbon radicals such as cyclohexyl, cyclopentyl, methylcyclohexyl and cyclohexenyl; aryl hydrocarbon radicals such as phenyl, xenyl, naphthyl, tolyl and xylyl and aralkyl hydrocarbon radicals such as benzyl, beta-phenylethyl and beta-phenylpropyl. R can also be any radical of the formula RCH CH in which R is a perfiuoroalkyl radical such as trifluoromethyl, pentafluoroethyl, heptafluoropropyl or C F For the purpose of this invention, x can be hydrogen or hydroxyl or any hydrocarbonoxy radical such as methoxy, ethoxy, octadecyloxy or isopropoxy; and alkenyloxy radical such as allyloxy or octadecenyloxy or any alkoxyalkoxy radical such as beta-methoxy ethoxy, beta-ethoxy ethoxy or CH O(CH CH O) In other words, the term hydrocarbonoxy as used herein means a radical composed of C, H and oxygen in which the latter is either in the form of a COC linkage or a CO-linkage in which the other valence of the O is attached to a Si atom.

R can be any monovalent hydrocarbon radical such as those specifically shown for R above together with any monovalent halohydrocarbon radical such as chloromethyl, gamma-chloropropyl, chlorovinyl, perfluorovinyl, chlorophenyl, bromophenyl, ot,oc,oz-tIifi1101'Ot0lyl, chloroxenyl, bromo cyclohexyl, fluoro cyclohexenyl, hexafluoro cyclopentyl and trifluoropropyl.

As can be seen, the R" siloxane units shown herein can be Of the formula R SiO R" SiO, R"SIO1 5 Or units. Thus, the copolymers of this invention can be fluid, elastome'ric or resinous materials depending upon the ratio of R" groups to silicon in the composition.

The following examples are illustrative only and should not be construed as limiting the invention which is properly delineated in the appended claims. The following abbreviations are used below, Ph for phenyl and Me for methyl.

Example 1 24.3 g. of magnesium chips were dried in an atmosphere of nitrogen at 100 C. for one hour. A mixture of 94.6 g. of dimethylchlorosilane and ml. of tetrahydrofuran were added to the magnesium. 20 m1. of a solution of 80.5 g. of o-chlorobenzyl chloride in 200 m1. of tetrahydrofuran was added and the mixture was warmed to 33 C. at which temperature the reaction was initiated with a small lump of p-dibromobenzene. It was necessary to maintain the reaction at a temperature of about 68 C. as the remainder of the o chlorobenzyl chloride solution was added dropwise over a period of 4 hours. Refluxing solution was dried by azeotroping the water and the product was fractionally distilled to give a fluid material boiling 120 C. at 30 mm. This material had the formula CH was continued for 4 hours and the mixture stood at room 5 temperature overnight. The mixture was then heated at J) a temperature of 72-74 C. for 5 hours. The reaction product was poured over crushed ice and filtered to remove unreacted magnesium. It was then washed to neu- I trality with water and 'fractionally distilled to give the compound This compound had a refractive index at 25 C. of 1.4961

Me: and a density of 25 C. of 0.9664. CHRSiH Example 3 13.3 g. of octamethylcyclotetrasiloxane and 1 g. of CH: Me: SIiMG having the following properties. Boiling point 117 C. at mm., n 1.5080 and d 0.889. 20 sli Example 2 .4 g. of crushed dry KOH was dissolved in 140 ml. of were mixed with a small amount of potassium dimethyl absolute ethanol and 8 ml. of water by refluxing. 32.1 g. silanolate catalyst and heated at 150 C. for two hours. of 25 The product was diluted with benzene and precipitated with methanol. The polymer thus isolated was dried in a CH vacuum, devolatilized and filtered through Celite. The 1 product was a fluid having a viscosity of 978 cs. at 28 C. SH and a refractive index at 25 C. at 1.4070. The product 30 was a copolymer of 2.5 mol percent Meg o I I was added dropwise to the refluxing alcohohc alkali over CH l a period of two hours. During this time, the quantitative amount of hydrogen was collected. After the gas evolu- Mel tion had stopped, the mixture was allowed to reflux an units and 97.5 mol percent dimethylsiloxane units. additional half hour so as to complete the condensation EX 1 4 of the intermediate diol amp 6 Meg When the following silanes are reacted with o-chloro- 40 benzylchloride in accordance with the procedure of Ex- CHISlOH ample l, the following products are obtained. In the formulae below A is the SIrOH Me; CH:- radical The material was diluted with 150 m1. of benzene and washed with ml. portions of water until neutral. The

Sllane Product Ph Ph CH2=CHS i(OMe) (Cl) CraHavSi-(O CHgOHzOMe) (Cl) (GOHCHOSKOCnHJ-MCI) S1(Ci8H:7)(0 CHgCHgOMe) K iaHn) (O CH CHgOMe) Sllane Product Si(O CHMez) (Cl) SIP-(Q) o HMe A s1-( )(OCHMe,)

Example 5 When the products of Example 4 are hydrolyzed with .1% acetic acid solution the following diols are obtained.

S l-(CH=CH2) (OH) Sl(CH=CHn) (OH) l b i ci s'nomomom Me I Example 6 When the diols of Example 5 are condensed in accordance with the procedure of Example 2, the following cyclic compounds are obtained.

/Csa

Si(Ph) (CH=CH2) l a, Si/ 2 SKCHSCHZCHFQI Example 7 When the diol Mei I CHgSiOH SiOH is heated with sodium .phenoxide at 100 C., a polymer of the unit formula When an equimolar mixture of the diols e 1"" CHaSiOH OHzSiOH and SIiOH SIiOH Me: P 2

small amount of KOH with the following silanes the following copolymers are obtained. The copolymer unit -S|i HzSiO- M9: M62

is represented by the numeral (1).

Sllanes Copolymer 50 mol percent 50 mol percent (1) CH=CH3 50 mol percent (Me) (CH;=CH) S10 MeSi(OMe),

10 mol percent CmH31Si(OMe); 10 mol percent CBHUSIOIJ 10 mol percent Me SiOMe 10 mol percent Me SiO.

mol percent 40 mol percent lrie Ill/Io 30 mol percent 30 mol percent PhSi(OMe);

10 mol percent CFzCHzCHgSKOMO):

10 mol percent Cl S1(OMe):

10 mol percent C1(CH:)3S1(OM6):

60 mol percent lYIe Cl Si(OMe)z 10 mol percent Sl(0Et)4 mol percent MezSiOMe PhSiO Me 10 mol percent (1) 10 mol percent CF;CH;OH;Sl01.

10 mol percent 010531014 10 mol percent C1(CH,);S1O

60 mol percent ltlde 10 mol percent (1) 10 mol percent SiOa 45 mol percent Me;SiO. 45 mol percent (1) That which is claimed is: 45 1. A composition of the formula is heated with sodium phenoxide in tetralin a copolymer of 50 mol percent -Sii CHaS|iO Me; Me: and 50 mol percent -Si CH S|iO- ha P11: is obtained.

Example. 9* When the compound h lea OHgSiOMe SiOMe is cohydrolyzed and co-condensed in the presence of a 75 2 C HgSiX SiX in which R is selected from the group consisting of monovalent hydrocarbon radicals and radicals of the formula RCH CH where R is a perfluoroalkyl radical and X is selected from the group consisting of hydrogen, hydroxyl and hydrocarbonoxy radicals.

2. A composition in accordance with claim 1 where each R is methyl and each X is hydrogen. 3. A compound of the formula in which R is selected from the group consisting of monovalent hydrocarbon radicals and radicals of the formula R'CH CH in which R is a perfluoroalkyl radical.

4. Composition in accordance with claim 2 in which each R is methyl.

9 10 5. A polymeric siloxane having at least one unit of hydrocarbon radicals and n is an integer from 0 to 3 the formula inclusive.

6. A copolymer in accordance with claim 5 in which R2 each R and each R" is methyl.

I (JHZSIO References Cited in which R is selected from the group consisting of mono- UNITED T F PATENTS valent hydrocarbon radicals and radicals of the formula 3,050,542 8/1962 P109011- R'CI-I CH in which R is a perfluoroalkyl radical, any 3,150,115 9/ 1964 Clark et 260-4481 XR remaining units in said polymer being of the formula 10 3,175,993 3/1965 Weyenberg 260448-2 XR Rnnsio 3,304,320 2/1967 Spencer.

T TOBIAS E. LEVOW, Primary Examiner.

in which R is selected from the group consisting of 15 F SHAVER Assistant Examiner monovalent hydrocarbon radicals and monovalent halo- 

1. A COMPOSITION OF THE FORMULA 